Hydroformylation process and bisphosphite compound used therein

ABSTRACT

A hydroformylation process for preparing a hydroformylated product by reacting an olefinic compound with hydrogen and carbon monoxide in the presence of a Group VIII metal catalyst, in the reaction of which there is present a phosphite compound having the formula (I), ##STR1## wherein R 1  and R 2  are respectively an aromatic hydrocarbon groups which may be the same or different and the aromatic hydrocarbon group has at least a hydrocarbon group on a carbon atom adjacent to a carbon atom bonded with an oxygen atom as a substituent; A 1  is an n-valent organic group having an aliphatic hydrocarbon group, a cycloaliphatic hydrocarbon group or an aromatic hydrocarbon group bonded with an adjacent oxygen atom, which may respectively have a substituent; n is an integer of from 2 to 4; and the respective [--O--P(OR 1 )(OR 2 )] group may be the same or different.

This is a division, of application Ser. No. 07/895,676, filed on Jun. 9,1992, now U.S. Pat. No. 5,235,113.

The present invention relates to a hydroformylation process of anolefinic compound using a modified Group VIII metal catalyst.

It is well known in the art to produce an aldehyde or its hydrogenatedproduct, i.e. alcohol, by reacting an olefinic compound with hydrogenand carbon monoxide in the presence of a modified Group VIII metalcatalyst.

As the catalyst, a soluble complex of a Group VIII transitionmetal-phosphorus ligand is generally used, and it is well known that theligand used with this metal component has a substantial influence on thecatalytic reaction. It is also well known that reaction activity,selectivity or catalyst stability largely varies in hydroformylationreaction depending on the selection of the ligand, and it is animportant subject in this technical field to make a research on a ligandeffective for improving these properties.

Various phosphite compounds are known as a group of phosphorus compoundsused for a ligand, and phosphite compounds such as a polyphosphitehaving plural coordinated phosphorus atoms in a molecule have beenheretofore proposed in addition to simple monophosphite compounds suchas a trialkylphosphite and a triarylphosphite.

For example, Japanese Unexamined Patent Publication No. 116587/1987 orNo. 116535/1987 discloses a phosphite compound characterized by thestructure wherein at least one phosphorus atom is bonded with adjacenttwo oxygen atoms to form a ring, as a phosphite compound containing atleast 2 phosphorus atoms in a molecule.

As mentioned above, various phosphite compounds have been proposed as aligand used in hydroformylation reaction, but the stability of the priorphosphite compound has not been always satisfactory in the reactionprocess and the prior phosphite still has a problem when it is used asan industrial catalyst which is requested to maintain its catalyticactivity for a long term. Thus, the development of a phosphite ligandexcellent in hydroformylation activity, selectivity of the aimed productand catalyst stability is strongly demanded.

The present inventors have studied and made a research for a ligandeffective for improving and maintaining activity and selectivity inhydroformylation reaction, and as the result of the research, havediscovered that a phosphite compound having the specific structure iseffective for hydroformylation and has an excellent catalyst stability.The present invention has been achieved on the basis of this discovery.

Thus, the present invention provides a hydroformylation process forpreparing a hydroformylated product by reacting an olefinic compoundwith hydrogen and carbon monoxide in the presence of a Group VIII metalcatalyst, characterized in that there is present in the reaction systema phosphite compound having the formula (I), ##STR2## wherein R¹ and R²are respectively an aromatic hydrocarbon group which may be the same ordifferent and the aromatic hydrocarbon group has at least a hydrocarbongroup on a carbon atom adjacent to a carbon atom bonded with an oxygenatom as a substituent; A¹ is an n-valent organic group having analiphatic hydrocarbon group, a cycloaliphatic hydrocarbon group or anaromatic hydrocarbon group bonded with an adjacent oxygen atom, whichmay respectively have a substituent; n is an integer of from 2 to 4; andthe respective [--O--P(OR¹)(OR²)] group may be the same or different,and also provides a bisphosphite compound having the formula (II),##STR3## wherein R³, R⁴, R⁵ and R⁶ are respectively a β-naphthyl grouphaving a hydrocarbon group at least at the 3-position, which may be thesame or different, and A² is a divalent group having an aliphatichydrocarbon group, a cycloaliphatic hydrocarbon group or an aromatichydrocarbon group bonded with an adjacent oxygen atom, which mayrespectively have a substituent.

The present invention is described hereinafter in more details.

The phosphite compounds used in the hydroformylation process of thepresent invention are defined by the above general formula (I). Amongthese phosphite compounds, a bisphosphite compound defined by the abovegeneral formula (II) is novel.

In the above formula (I), examples of aromatic hydrocarbon groupsrepresented by R¹ and R² include a phenyl group, a naphthyl group, ananthracenyl group or the like, and among them, a phenyl group and aβ-naphthyl group are preferable for industrial use.

The aromatic hydrocarbon groups represented by R¹ and R² have ahydrocarbon substituent on a carbon atom adjacent to a carbon atombonded with an oxygen atom, and examples of the hydrocarbon substituent(e.g. a substituent present at the ortho-position of a phenyl group ofR¹ and R² or a substituent present at the 3-position of a β-naphthylgroup of R¹ and R²) include an alkyl group, an aralkyl group, an arylgroup, a cycloalkyl group or the like, and among them, preferableexamples include an alkyl group having a carbon number of from 3 to 20,particularly an isopropyl group, a tertiary butyl group, a tertiarypentyl group or the like.

R¹ and R² may have other substituents (preferably from 1 to 3) inaddition to the above substituents, and examples of these substituentsinclude a linear or branched alkyl group such as methyl, ethyl, propyl,butyl and pentyl, an alkoxy group such as methoxy and ethoxy, analkoxycarbonyl group such as methoxycarbonyl and ethoxycarbonyl, and aphenyl group.

Each group represented by the formula, ##STR4## may be the same ordifferent. That is, particular examples of the phosphite compoundsrepresented by the formula (I) include: ##STR5## wherein R¹¹, R¹², R¹³and R¹⁴ are as defined in the above R¹, and may be the same ordifferent; and R²¹, R²², R²³ and R²⁴ are as defined in the above R², andmay be the same or different.

Examples of the group A¹ in the above formula (I) include 1 an n-valentorganic group containing an aliphatic hydrocarbon group which may have asubstituent, 2 an n-valent organic group containing a cycloaliphatichydrocarbon group which may have a substituent, or 3 an n-valent organicgroup containing an aromatic hydrocarbon group which may have asubstituent.

Preferable examples of these groups include a divalent group representedby --R-- or --R--B--R--, a trivalent group represented by ##STR6## and atetravalent group represented by ##STR7## wherein R represents fromdivalent to tetravalent saturated aliphatic hydrocarbon groups, asaturated cycloaliphatic hydrocarbon group or an aromatic hydrocarbongroup, each group of which may have a substituent (examples of thesubstituent include an alkoxy group, a phenyl group, a naphthyl group,an amino group, an alkylamino group, an acyl group, an alkoxycarbonylgroup, an acyloxy group or the like); and B represents a group selectedfrom the group consisting of --CR⁷ R⁸ --, --O--, --S-- and --CO-- (eachof R⁷ and R⁸ is a group selected from the group consisting of a hydrogenatom, an alkyl group, an aryl group, an arylalkyl group, an alkylarylgroup and a cycloalkyl group).

Preferable examples of R include: ##STR8## a phenylene group, abiphenylene group, a naphthylene group or the like.

When the phosphite compound is a bisphosphite compound as defined by theabove general formula (II), A² in the above formula (II) represents adivalent group containing an aliphatic hydrocarbon group, acycloaliphatic hydrocarbon group or an aromatic hydrocarbon group bondedwith an adjacent oxygen atom. Preferable examples of the divalent grouprepresented by A² include --Ar-- and --Ar--B--Ar-- wherein Ar is anarylene group which may have a substituent, and B is a group selectedfrom the group consisting of --CR⁹ R¹⁰ --, --O--, --S--, and --CO--(each of R⁹ and R¹⁰ is a group selected from the group consisting of ahydrogen atom, an alkyl group, an aryl group, an arylalkyl group, analkylaryl group and a cycloalkyl group). Preferable examples of Arinclude a phenylene group, a biphenylene group, a naphthylene group orthe like.

A method for preparing the phosphite compounds of the formulas (I) and(II) is not specially limited. For example, the phosphite compound ofthe formula (I) can be easily prepared by (a) reacting phosphorustrichloride with an aromatic hydrocarbon compound containing ahydrocarbon group on a carbon atom adjacent to a carbon atom having aphenolic hydroxyl group in a solvent such as toluene in the presence ofan amine compound to form an intermediate product of the formula,ClP(OR¹) (OR²) wherein R¹ and R² are the same as defined in the aboveformula (I), and (b) then reacting the formed intermediate product witha compound of the formula A¹ (OH)_(n) wherein A¹ and n are the same asdefined in the above formula (I), to form a corresponding phosphitecompound.

The bisphosphite compound of the formula (II) can also be easilyprepared, for example, by (a) reacting phosphorus trichloride with aβ-naphthol compound having a hydrocarbon group at the 3-position in asolvent such as toluene in the presence of a HCl receptor such as anamine to form an intermediate product of the formula, ClP(OR³)(OR⁴) orClP(OR⁵) (OR⁶) wherein R³, R⁴, R⁵ and R⁶ are the same as defined in theabove general formula (II), and (b) then reacting the formedintermediate product with a divalent phenol compound of the formula, A²(OH)₂ wherein A² is the same as defined in the above formula (II), toform a corresponding bisphosphite compound.

Examples of the compounds of the formula, A¹ (OH)_(n) or A² (OH)₂,include 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone,2,5-dimethylhydroquinone, 4,6-di-t-butylresorcinol, bisphenol-A,4,4'-methylenebis(2-methyl-6-t-butylphenol),4,4'-thiobis(2-methyl-6-t-butylphenol),4,4'-oxobis(3-methyl-6-isopropylphenol),4,4'-butylidenebis(3-methyl-6-t-butylphenol), 2,2'-biphenyldiol, 3,3',55'-tetramethyl-2,2'-biphenyldiol, 3,3',55'-tetra-t-butyl-2,2'-biphenyldiol,3,3'-dimethoxy-5,5'-dimethyl-2,2'-biphenyldiol,3,3'-di-t-butyl-5,5'-dimethoxy-2,2'-biphenyldiol,3,3'-di-t-butyl-5,5'-dimethyl-2,2'-biphenyldiol,2,2'-dihydroxydiphenylmethane,2,2'-methylenebis(4-methyl-6-t-butylphenol),2,2'-methylenebis(4-ethyl-6-t-butylphenol),2,2'-thiobis(4-methyl-6-t-butylphenol),2,2'-thiobis(4-t-butyl-6-methylphenol),2,2'-thiobis(4,6-di-t-butylphenol), 1,1'-thiobis(2-naphthol), catechol,2,3-dihydroxynaphthalene, 1,8-dihydroxynaphthalene,1,4-dihydroxynaphthalene, phloroglucin, 1,1'-methylenebis(2-naphthol),1,1'-di-2-naphthol, ethyleneglycol, 1,3-propanediol, 1,2-butanediol,1,4-butanediol, pentaerythritol, trans- 1,2-cyclohexanediol,cis-1,2-cyclohexanediol, cis-1,2-cyclohexanedimethanol,cis-1,2-cyclododecanediol or the like.

Examples of the aromatic hydrocarbon compound having a hydrocarbon groupon a carbon atom adjacent to a carbon atom having a phenolic hydroxyl orthe β-naphthol compound having a hydrocarbon group at the 3-position,include 2-t-butylphenol, 2,4-di-t-butylphenol, 2-isopropylphenol,2-t-amylphenol, 2,4-di-t-amylphenol, 2-s-butylphenol,6-t-butyl-2,4-xylenol, 3-t-butyl-4-hydroxyanisol3-t-butyl-4-hydroxybiphenyl, 2-t-butyl-p-cresol, methyl3-t-butyl-4-hydroxybenzoate, 2-hydroxybiphenyl, 3-t-butyl-2-naphthol,3,6-di-t-butyl-2-naphthol, 3,6,8-tri-t-butyl-2-naphthol,3-isopropyl-2-naphthol, 3,6-diisopropyl-2-naphthol,3,6,8-triisopropyl-2-naphthol, 3-t-amyl-2-naphthol,3,6-di-t-amyl-2-naphthol, 3,6,8-tri-t-amyl-2-naphthol or the like.

The phosphite compound used in the present invention has such structuralcharacteristics that it does not contain a ring structure formed byadjacent two oxygen atoms and a phosphorus atom and that the aromatichydrocarbon group represented by R¹ and R² in the formula (I) has ahydrocarbon group on a carbon atom adjacent to a carbon atom bonded withan oxygen atom. Due to these structural characteristics, it can bepresent in the hydroformylation reaction at a high stability as aphosphite ligand and a complex comprising Group VIII metal-phosphiteligand, and as this result, it provides a satisfactory hydroformylationactivity and selectivity.

When A¹ in the formula (I) is an organic group containing an aromatichydrocarbon group or when A² in the formula (II) is a divalent groupcontaining an aromatic hydrocarbon group, the aromatic hydrocarbon groupshould preferably have a substituent on a carbon atom adjacent to acarbon atom bonded with an oxygen atom. The substituent used hereinmeans every substituent other than a hydrogen atom, examples of whichinclude --OP(OR¹) (OR²), --OP(OR³) (OR⁴) or --OP(OR⁵)(OR⁶); --B--R-- or##STR9## (as in the case that A¹ is the above mentioned --R--B--R-- or##STR10## or --B--Ar-- (as in the case that A² is the above mentioned--Ar--B--Ar--). Also, in the case of the bisphosphite compounds of theformula (II), four β-naphthyl groups should preferably have a bulkyhydrocarbon group at the 3- and 6-positions.

When the phosphite compound of the present invention is used in thehydroformylation reaction of an olefinic compound in the presence of aGroup VIII metal catalyst, the activity or the selectivity of the aimedproduct in the hydroformylation reaction can be controlled by selectingthe type of the phosphite compounds. For example, when the phosphitecompound has such a structure as to form a chelate type metal complexwith the Group VIII metal, the hydroformylated product provides a highn-form selectivity in the hydroformylation of α-olefin. Examples of ann-valent compound of the formula, ##STR11## (wherein A¹ and n are thesame as defined in the above formula (I)) used in the preparation of thephosphite compound, suitable for forming this chelate type phenoliccomplex, include 2,2'-biphenyldiol, 2,2'-dihydroxydiphenylmethane,2,3-dihydroxynaphthalene, catechol, 1,2-cyclohexanediol,cis-1,2-cyclododecanediol, ethyleneglycol, 1,3-propanediol,pentaerythritol, 1,1'-thiobis(2-naphthol), 1,1'-dinaphthol,2,3-dihydroxynaphthalene or the like.

When the phosphite compound has such a structure as to form anon-chelate type metal complex with the Group VIII metal, it provides ahigh hydroformylation activity not only to an α-olefin but also to abranched internal olefin having. Examples of an n-valent compound of theformula, ##STR12## (wherein A¹ and n are the same as defined in theabove formula (I)) used in the preparation of the bisphosphite compound,suitable for forming the non-chelate type metal complex, include2,5-di-t-butylhydroquinone, 4,4'-methylenebis(2-methyl-6-t-butylphenol),4,4'-thiobis(2-methyl-6-t-butylphenol), 2,5-di-t-amylhydroquinone,4,4'-butylidenebis(2-methyl-6-t-butylphenol) or the like.

Typical examples of the phosphite compounds of the formula (I) or (II)used in the hydroformylation process of the present invention areillustrated in the following. In this case, it is preferable forobtaining a high stability that when A¹ or A² has an aromatichydrocarbon ring bonded with an adjacent oxygen atom, the aromatichydrocarbon ring should preferably have such a bulky hydrocarbon groupas an isopropyl group, a t-butyl group or a t-pentyl group, on a carbonatom adjacent to a carbon atom bonded with an oxygen atom. ##STR13##

In the above chemical structural formulas,

is a tertiary butyl group;

is an isopropyl group;

is a tertiary amyl group;

Me is a methyl group; and

Et is an ethyl group.

An olefinic compound used in the preparation of aldehydes in accordancewith the present invention is not specially limited so long as it has atleast one olefinic double bond in the molecule, examples of whichinclude an olefinic compound substituted with a saturated hydrocarbongroup only, an olefinic compound substituted with a hydrocarbon groupcontaining an unsaturated hydrocarbon group, an olefinic compoundsubstituted with a functional group containing a heteroatom, and thelike.

Examples of the olefinic compound substituted with a saturatedhydrocarbon group only, include linear terminal olefinic hydrocarbonssuch as ethylene, propylene, 1-butene, 1,3-butadiene, 1-pentene,1-hexene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene,1-hexadecene, 1-octadecene, 1-eicosene and 1-dococene; branched terminalolefinic hydrocarbons such as isobutene and 2-methyl-1-butene; linearinternal olefinic hydrocarbons such as cis- and trans-2-butene, cis- and-trans-2-hexene, cis- and -trans-3-hexene, cis- and trans-2-octene andcis- and trans-3-octene; branched internal olefinic hydrocarbons such as2,3-dimethyl-2-butene, 2-methyl-2-butene and 2-methyl-2-pentene;terminal olefinic hydrocarbon-internal olefinic hydrocarbon mixturessuch as octenes prepared by dimerization of butenes, olefin oligomerisomer mixtures of from dimer to tetramet of lower olefins includingpropylene, n-butene, isobutene or the like; and cycloaliphatic olefinichydrocarbons such as cyclopentene, cyclohexene, 1-methylcyclohexene,cyclooctene and limonene.

Examples of the olefinic compound substituted with a hydrocarbon groupcontaining an unsaturated hydrocarbon group include olefinic compoundscontaining an aromatic substituent such as styrene, α-methylstyrene andallylbenzene; and diene compounds such as 1,5-hexadiene, 1,7-octadieneand norbornadiene.

Examples of the olefinic compound substituted with a functional groupcontaining a heteroatom include vinyl methyl ether, methyl oleate, allylalcohol, oleyl alcohol, 3-methyl-3-butene-1-ol, 3-hydroxy-1,7-octadiene,1-hydroxy-2,7-octadiene, 1-methoxy-2,7-octadiene, 7-octene-1-al,hexa-1-en-4-ol, acrylonitrile, acrylic acid esters such asmethylacrylate, methacrylic acid esters such as methylmethacrylate,vinyl acetate and 1-acetoxy-2,7-octadiene.

The amount of the phosphite compound of the present invention is notspecially limited, but is optionally selected so that favorable resultscan be obtained in respect of catalyst activity and selectivity.Generally, the phosphite compound of the present invention is used in anamount of from about 0.5 to 500 mols, preferably from 1 to 100 mols pergram atom of Group VIII metal.

The phosphite compound of the present invention is preferably used bypreviously forming a complex with a Group VIII metal compound. The GroupVIII metal complex can be easily prepared from the phosphite compoundsand the Group VIII compounds such as hydrides, halides, organic acidsalts, inorganic acid salts, oxides, carbonyl compounds and aminecompounds, in accordance with a known complex-forming method. Also, thecomplex may be formed in situ by charging the Group VIII metal compoundsand the phosphite compounds into the hydroformylation reaction zone.

Examples of the Group VIII metal compounds include ruthenium compoundssuch as Ru₃ (CO)₁₂, Ru(NO₃)₃, RuCl₃ (Ph₃ P)₃ and Ru(acac)₃ ; palladiumcompounds such as PdCl₂, Pd(OAc)₂, Pd(acac)₂, PdCl₂ (COD) and PdCl₂ (Ph₃P)₂ ; osmium compounds such as Os₃ (CO)₁₂ and OSCl₃ ; iridium compoundssuch as Ir₄ (CO)₁₂ and IrSO₄ ; platinum compounds such as K₂ PtCl₄,PtCl₂ (PhCN)₂ and Na₂ PtCl₆ ·6H₂ O; cobal compounds such as CoCl₂,Co(NO₃)₂, Co(OAc)₂ and Co₂ (CO)₈ ; and rhodium compounds such as RhCl₃,Rh(NO₃)₃, Rh(OAc)₃, Rh₂ O₃, Rh(acac) (CO)₂, [Rh(OAc) (COD)]₂, Rh₄(CO)₁₂, Rh₆ (CO)₁₆, RhH(CO) (Ph₃ P)₃, [Rh(OAc) (CO)_(2]2) and[RhCl(COD)]₂ (wherein "acac" is an acetylacetonate group; "Ac" is anacetyl group; "COD" is 1,5-cyclooctadiene; and "Ph" is a phenyl group).However, it should be noted that the Group VIII metal compounds are notnecessarily limited to the above listed compounds.

The amount of a Group VIII metal compound used is not specially limited,but is optionally selected so that favorable results can be obtained inrespect of catalyst activity and economy. Generally, it is used at aconcentration of from 0.05 mg to 5 g, preferably from 0.5 mg to 1 g (onthe basis of metal atom) per litter of an olefinic compound in thehydroformylation reaction zone.

In the hydroformylation reaction of the present invention, the use of areaction solvent is not essential, but a solvent inert to thehydroformylation reaction may be present. Suitable examples of thesolvent include aromatic hydrocarbon compounds such as benzene, toluene,xylene and dodecylbenzene; ketones such as acetone, diethylketone andmethylethylketone; ethers such as tetrahydrofuran and dioxane; andesters such as ethyl acetate and di-n-octyl phthalate. A mixture of thesolvents may also be used. It is also possible to use an excess amountof the starting olefinic compound as a solvent.

The reaction conditions to conduct the hydroformylation process of thepresent invention are the same as those used in the conventionalprocess. For example, the reaction temperature is from room temperatureto 200° C., preferably from 50° to 150° C., and the reaction pressure isfrom normal pressure to 200 atms, preferably from 5 to 100 atms, morepreferably from 5 to 50 atms. The mol ratio of hydrogen and carbon oxide(H₂ /CO) is generally from 10/1 to 1/10, preferably from 1 to 6/1.

Examples of the reaction system of the hydroformylation reaction includea continuous type, semi-continuous type or batch type operation using astirring type reaction tank or a bubble tower type reaction tank.

Another feature of the present invention resides in that since thephosphite compound of the present invention can be stably present afterthe hydroformylation reaction, the catalyst component containing thephosphite compound and the hydroformylated product are separated by aknown method and a part or the whole part of the catalyst component canbe reused by recycling into the hydroformylation reaction zone.

As mentioned above, according to the present invention, thehydroformylation reaction activity and the selectivity of the aimedproduct can be highly improved by getting the phosphite compoundtogether with the Group VIII metal catalyst present in thehydroformylation reaction. Furthermore, since the phosphite compound isfavorably stable, the catalyst containing the phosphite compoundrecovered by a known method can be reused in the hydroformylationreaction, thus providing a great industrial merit.

Now, the present invention will be described in further detail with thereference to Examples. However, it should be understood that the presentinvention is by no means restricted to such specific Examples.

EXAMPLE 1

90 ml of 1-octene, 10 ml of toluene (gas chromatography internalstandard), 2.6 mg of Rh(acac) (CO)₂ and 25 mols of the above mentionedPhosphite Compound No. 14 per mol of rhodium atom (P/Rh=50) were chargedin the atmosphere of argon into a stainless steel madeup-and-down-stirring type autoclave having an internal volume of 200 ml,and the autoclave was sealed. The autoclave was purged with nitrogen gas(30 kg/cm² ·G) three times, and the temperature was raised to 120° C.under nitrogen gas (0 kg/cm² ·G). Immediately after the temperaturereached 120° C., water gas (H₂ /CO=1) was charged therein under pressureto a level of 50 kg/cm² ·G to initiate reaction and the reaction wascontinued for 4 hours. The water gas consumed during the reaction wassupplied from a pressurized chamber through a secondary pressureregulator, and the reaction pressure was constantly maintained at 50kg/cm² ·G.

After the reaction, the autoclave was cooled to room temperature, andthe reaction liquor was taken out under argon atmosphere. A part of thereaction liquor was subjected to gas chromatography analysis (column:CBPl Capirary 0.25φ×50 m manufactured by Shimazu Seisakusho K. K.) tomeasure the concentration of the product. The results are shown in Table1.

The reaction liquor was further subjected to ³¹ P-nmr measurement (JEOLJNM-FX100), and as this result, a signal of a free phosphite compoundwas observed at chemical shift value δ=129.9 ppm under H₃ PO₄ standard,but other oxides and decomposed materials of the phosphite were notdetected.

COMPARATIVE EXAMPLE 1

The hydroformylation reaction of 1-octene was repeated in the samemanner as in Example 1, except that the phosphite compound (III) havingthe following structure was used in place of Phosphite Compound No. 14.The reaction results are shown in Table 1. ##STR14##

EXAMPLES 2 TO 4

The hydroformylation reaction of 1-octene was repeated in the samemanner-as in Example 1, except that each of Phosphite Compounds Nos. 33,37 and 39 was used in place of phosphite Compound No. 14. The reactionresults are shown in Table 1. According to the ³¹ P -nmr analysis of thereaction liquor, oxides and decomposed products of the phosphite werenot detected.

EXAMPLE 5

The hydroformylation reaction of 1-octene was repeated in the samemanner as in Example 1, except that Phosphite Compound No. 12 was usedin place of Phosphite Compound No. 14 and 26.0 mg of Rh(acac)(CO)₂ wasused at P/Rh mol ratio of 8, and that the reaction was continued for 7hours. The reaction results are shown in Table 1. According to the ³¹P-nmr analysis of the reaction liquor taken out after the reaction,decomposed materials of the phosphite compound were not detected.

EXAMPLE 6

The hydroformylation reaction of 1-octene was repeated in the samemanner as in Example 5, except that Phosphite Compound No. 35 was usedin place of Phosphite Compound No. 12. The reaction results are shown inTable 1. Even after the reaction, the phosphite compound was stablypresent.

                                      TABLE 1                                     __________________________________________________________________________           Phosphite                                                                           Reaction                                                                           Rh           Octene                                                                              C.sub.9 Aldehyde                         Experiment                                                                           compound                                                                            time concentration                                                                        P/Rh Mol                                                                            conversion                                                                          yield  C.sub.9 Aldehyde                  No.    No.   (hr) (mg/l) ratio (mol %)                                                                             (mol %)                                                                              n/i ratio                         __________________________________________________________________________    Example-1                                                                            (14)  4    10.4   50    86.0  85.4   10.8                              Comparative                                                                          --    4    10.4   50    88.0  87.2   2.6                               Example-1                                                                     Example-2                                                                            (33)  4    10.4   50    88.3  87.8   12.6                              Example-3                                                                            (37)  4    10.4   50    92.0  91.4   4.4                               Example-4                                                                            (39)  4    10.4   50    93.0  92.3   11.4                              Example-5                                                                            (12)  7    104     8    75.1  74.6   28.4                              Example-6                                                                            35)   7    104     8    80.0  79.5   65.7                              __________________________________________________________________________

EXAMPLE 7

The hydroformylation reaction was conducted for 5 hours in the samemanner as in Example 5, except that Phosphite Compound No. 2 was used atP/Rh mol ratio of 10 in place of Phosphite Compound No. 12 and that anoctene mixture of dimerized butene was used as the olefin startingmaterial. After the reaction, the octene conversion was 89.0 mol % andthe aldehyde Field was 88.4 mol %. According to the ³¹ P-nmr analysis ofthe reaction liquor, decomposed materials of the phosphite compound werenot detected and the phosphite compound was stably present.

EXAMPLE 8

55 ml of methaxylene, 5 ml of toluene, 15.0 mg of Rh(acac)(CO)₂ and 5mols of the above mentioned Phosphite Compound No. 12 per mol of rhodiumatom (P/Rh mol ratio=10) were charged under argon atmosphere into astainless steel made up-and-down-stirring type autoclave having aninternal volume of 200 ml, and the autoclave was sealed. The autoclavewas purged with nitrogen gas (30 kg/cm³ ·G) three times. After thepressure of the nitrogen gas was restored to 0 kg/cm² ·G, 16.0 g ofliquefied 1-butene was charged under pressure. Thereafter, thehydroformylation reaction of 1-butene was conducted in the same manneras in Example 1 under the conditions of H₂ /CO (mol ratio=1) 50 kg/cm²·G and temperature 120° C. After the reaction for 6 hours, the buteneconversion was 90.8 mol % and the aldehyde yield was 90.0 mol %, and then/i aldehyde production ratio was 20.3. Decomposed by-products of thephosphite compound were not detected from the reaction liquor.

EXAMPLE 9

The hydroformylation reaction of 1-butene was conducted in the samemanner as in Example 8, except that Phosphite Compound No. 14 was usedin place of Phosphite Compound No. 12 and that the amount ofRh(acac)(CO)₂ was made 1.5 mg and the P/Rh mol ratio was made 50. Afterthe reaction for 6 hours, the butene conversion was 98.0 mol % and thealdehyde yield was 97.3 mol %, and the n/i aldehyde production ratio was7.0. The phosphite compound was stably present even after used in thereaction.

EXAMPLE 10 (Synthesis of Phosphite Compound)

About 50 ml of toluene solution having 15.38 g (0.06 mol) of3,6-di-t-butyl-2-naphthol and 6.07 g (0.06 mol) of triethylaminedissolved, was dropwise added at room temperature for about 0.5 hourunder stirring into about 50 ml of a PCl₃ toluene solution having 4.11 g(0.03 mol) of phosphorus trichloride dissolved. After the dropwiseaddition, the resultant mixture was stirred further for one hour. To thereaction liquor containing the phosphorochloridite intermediate thusobtained, was dropwise added about 50 ml of a toluene solution having2.79 g (0.015 mol) of 2,2'-biphenyldiol and 3.04 g (0.03 mol) oftriethylamine dissolved at room temperature for about 0.5 hour understirring. After the dropwise addition, the stirring was furthercontinued, and the completion of the reaction was recognized by ³¹ P-nmr analysis. Thereafter, about 100 ml of distilled water was added todissolve a by-produced solid triethyl amine hydrochloride precipitate,and the resultant solution was settled to separate the organic phase andthe aqueous phase. The aqueous phase was further extracted twice with 50ml of toluene, and the extracted liquor was mixed with the organicphase. The resultant mixture was dried with anhydrous magnesium sulfateovernight. After removing the magnesium sulfate by a 0.2μmilliporefilter, the resultant mixture was concentrated by vacuumdistillation to obtain a residue. Thereafter, the residue wasrecrystallized with toluene/acetonitrile (1/20 volume ratio) to obtain awhite powdery solid bisphosphite compound (the above mentioned PhosphiteCompound No. 58).

In the same manner as above, the above mentioned Bisphosphite CompoundsNos. 53, 55, 56, 59, 68 and 69 were respectively prepared by using3,6-di-t-butyl-2-naphthol and the corresponding divalent phenolcompounds.

The chemical structures of the bisphosphite compounds thus obtained wereanalyzed by phosphorus-31 nuclear magnetic resonance spectrum method(JEOL JNM-FX100), elemental analysis method and SIMS mass analysismethod (M-2000A manufactured by Hitachi Seisakusho K. K.). Theanalytical data are shown in Table 2.

                                      TABLE 2                                     __________________________________________________________________________            .sup.31 p-NMR                                                                 data *1                                                                       chemical                  SIMS mass                                           shift                     spectrum                                    Bisphosphite                                                                          value                                                                              Elemental analysis   molecular                                   compound No.                                                                          (ppm)         C  H  P  S  ion mass                                    __________________________________________________________________________    (58)    128.0                                                                              Calculated value                                                                       79.59                                                                            7.95                                                                             4.89                                                                             -- 1268 [M+]                                                Analytical value                                                                       79.29                                                                            8.05                                                                             4.75                                                                             --                                             (68)    129.2                                                                              Calculated value                                                                       79.66                                                                            8.02                                                                             4.83                                                                             -- 1281 [M+]                                                Analytical value                                                                       79.20                                                                            8.31                                                                             4.67                                                                             -- --                                          (59)    127.2                                                                              Calculated value                                                                       78.62                                                                            8.12                                                                             5.20                                                                             -- 1191 [M+]                                                Analytical value                                                                       78.60                                                                            8.06                                                                             5.17                                              (69)    128.9                                                                              Calculated value                                                                       79.32                                                                            7.96                                                                             4.99                                                                             -- 1242 [M+]                                                Analytical value                                                                       79.11                                                                            7.90                                                                             5.03                                                                             --                                             (53)    128.8                                                                              Calculated value                                                                       79.23                                                                            8.66                                                                             4.75                                                                             -- 1304 [M+]                                                Analytical value                                                                       79.08                                                                            8.75                                                                             4.71                                                                             --                                             (56)    130.1                                                                              Calculated value                                                                       79.36                                                                            8.78                                                                             4.65                                                                             -- 1332 [M+]                                                Analytical value                                                                       78.00                                                                            8.88                                                                             4.69                                                                             --                                             (55)    128.3                                                                              Calculated value                                                                       78.41                                                                            8.40                                                                             4.30                                                                             2.23                                                                             1440 [m+]                                                Analytical value                                                                       78.72                                                                            8.59                                                                             4.31                                                                             2.23                                           __________________________________________________________________________     *1: ppm to H.sub.3 PO.sub.4                                              

EXAMPLE 11

90 ml of 1-octene, 10 ml of toluene (gas chromatography internalstandard), 26.0 mg of Rh(acac) (CO)₂ and 4 mols of the above mentionedBisphosphite Compound No. 58 per mol of rhodium atom (P/Rh=8 equivalent)were charged in the atmosphere of argon into a stainless steel made upand down-stirring type autoclave having an internal volume of 200 ml,and the autoclave was sealed. The autoclave was purged with nitrogen gas(20 kg/cm² ·G) three times, and the temperature was raised to 120° C.under nitrogen gas (0 kg/cm² ·G). Immediately after the temperaturereached 120° C., water gas (H₂ /CO=1) was charged therein under pressureto a level of 50 kg/cm² ·G to initiate reaction and the reaction wascontinued for 6 hours. The water gas consumed during the reaction wassupplied from a pressurized chamber through a secondary pressureregulator, and the reaction pressure was constantly maintained at 50kg/cm² · G. After the reaction, the reaction liquor was taken out underargon atmosphere, and a part of the reaction liquor was subjected to gaschromatography analysis (column: Thetmon-3000 Capirary 0.25φ×50 m) tomeasure the concentration of the product. The octene conversion was 82.9mol % and the aldehyde yield was 81.7 mol %, and the n/i aldehydeproduction ratio was 23.3. The reaction liquor was further subjected to³¹ P-nmr analysis, but oxides and decomposed materials of the phosphitewere not detected.

EXAMPLE 12

The hydroformylation reaction of 1-octene was repeated in the samemanner as in Example 11, except that Bisphosphite Compound No. 68 wasused in place of Bisphosphite Compound No. 58 and 2.60 mg ofRh(acac)(CO)₂ was used at P/Rh mol ratio of 50. The octene conversionwas 90.0 mol % and the aldehyde yield was 89.6 mol %, and the n/ialdehyde production ratio was 9.0. Decomposed materials of the phosphitecompound were not detected.

EXAMPLE 13

The hydroformylation reaction of 1-octene was repeated in the samemanner as in Example 12, except that Bisphosphite Compound No. 59 wasused in place of Bisphosphite Compound No. 68. The octene conversion was90.0 mol % and the aldehyde yield was 89.6 mol %, and the n/i aldehydeproduction ratio was 13.0. Decomposed materials of the phosphitecompound were not detected.

EXAMPLE 14

The hydroformylation reaction of 1-octene was repeated in the samemanner as in Example 12, except that Bisphosphite Compound No. 69 wasused in place of Bisphosphite Compound No. 68. The octene conversion was89.0 mol % and the aldehyde yield was 88.3 mol %, and the n/i aldehydeproduction ratio was 15.7.

EXAMPLE 15

90 ml of an octene mixture of dimerized butene, 10 ml of m-xylene(internal standard), 24.6 mg of Rh(acac)(CO)₂ and 5 mols of the abovementioned Phosphite Compound No. 53 per mol of rhodium atom (P/Rh molratio=10 equivalent) were charged under argon atmosphere into astainless steel made up and down-stirring type autoclave having aninternal volume of 200 ml. Thereafter, the hydroformylation reaction ofthe mixed octene was conducted in the same manner as in Example 11 underthe conditions of H₂ /CO (mol ratio=1) 50 kg/cm² ·G and temperature 130°C. After the reaction for 5 hours, the octene conversion was 91.8 mol %and the aldehyde yield was 90.9 mol %. According to the ³¹ P-nmranalysis of the reaction liquor, decomposed products of the phosphitecompound were not detected.

EXAMPLE 16

The hydroformylation reaction of the mixed octene was repeated in thesame manner as in Example 15, except that Bisphosphite Compound No. 56was used in place of Bisphosphite Compound No. 53. After the reactionfor 5 hours, the octene conversion was 88.8 mol % and the aldehyde yieldwas 87.6 mol %. Even after the reaction, the bisphosphite compound wasstably present.

EXAMPLE 17

The hydroformylation reaction of the mixed octene was repeated in thesame manner as in Example 15, except that Bisphosphite Compound No. 55was used in place of Bisphosphite Compound No. 53. After the reactionfor 5 hours, the octene conversion was 91.4 mol % and the aldehyde yieldwas 90.3 mol %. Even after the reaction, the bisphosphite compound wasstably present.

EXAMPLE 18

55 ml of methaxylene, 5 ml of toluene, 15.0 mg of Rh(acac)(CO)₂ and 5mols of the above mentioned Phosphite Compound No. 58 per mol of rhodiumatom (P/Rh mol ratio=10 equivalent) were charged under argon atmosphereinto a stainless steel made up and down-stirring type autoclave havingan internal volume of 200 ml, and the autoclave was sealed. Theautoclave was purged with nitrogen gas (20 kg/cm³ ·G) three times. Afterthe pressure of the nitrogen gas was restored to 0 kg/cm² ·G, 15.9 g of1-butene was charged under pressure. Thereafter, the hydroformylationreaction of 1-butene was conducted in the same manner as in Example 11under the conditions of H₂ /CO (mol ratio=1) 50 kg/cm² ·G andtemperature 120° C. After the reaction for 7 hours, the buteneconversion was 89.3 mol % and the n/i aldehyde production ratio was18.9. According to the ³¹ P-nmr analysis of the reaction liquor, oxidesand decomposed products of the bisphosphite compound were not detectedfrom the reaction liquor.

EXAMPLE 19

The hydroformylation reaction of 1-butene was repeated in the samemanner as in Example 18, except that Bisphosphite Compound No. 68 wasused in place of Bisphosphite Compound No. 58 and 1.5 mg ofRh(acac)(CO)₂ was used. After the reaction for 6 hours, the buteneconversion was 99.9 mol % and the n/i aldehyde production watio was 6.8.Decomposed by-products of the bisphosphite compound were not detectedfrom the reaction liquor.

EXAMPLE 20

The hydroformylation reaction of 1-octene was repeated in the samemanner as in Example 12, except that 1,7-octadiene was used in place of1-octene and P/Rh mol ratio was made 100. After the reaction for 5hours, the octadiene conversion was 99.0 mol % and the diformylatedproduct (decanedial) yield was 80.0 mol %, and the n-form selectivityamong the diformylated product was 80.6 mol %.

COMPARATIVE EXAMPLE 2

90 ml of 1-octene, 10 ml of toluene (gas chromatography internalstandard), 2.5 mg of Rh(acac) (CO)₂ and 10 mols of the phosphitecompound having the following structure per mol of rhodium atom werecharged in the atmosphere of nitrogen into a stainless steel made up anddown-stirring type autoclave having an internal volume of 200 ml. Theautoclave was purged with nitrogen gas (30 kg/cm² ·G) three times, andthe temperature was raised to 120° C. under stirring after the internalpressure was restored to 0 kg/cm² ·G. Immediately after the temperaturereached 120° C., water gas (H₂ /CO=1) was charged therein under pressureto a level of 50 kg/cm² ·G from a pressurized chamber having an internalvolume of 200 ml through a secondary pressure regulator to initiatereaction and the reaction was continued for 5 hours. The internalpressure was constantly maintained at 50 kg/cm² ·G during the reaction.

After the reaction, the autoclave was cooled to room temperature and waspurged to normal pressure, and the reaction liquor was taken out. Aminor amount of the reaction liquor was subjected to gas chromatographyanalysis (column: C-BPl Capirary Column 0.25φ×50 m manufactured byShimazu Seisakusho K. K.) to measure the concentration of the product.As this result, the octene conversion was 30.3 mol % and the C₉ aldehydeyield was 29.6 mol %, and the n/i C₉ aldehyde production ratio was 2.2.##STR15##

EXAMPLE 21

90 ml of 1-tetradecene ("Dialene 14" Registered Trademark of MitsubishiKasei Corporation), 10 ml of toluene (gas chromatography internalstandard), 2.5 mg of Rh(acac)(CO)₂ and 50 mols of Phosphite Compound No.68 per mol of rhodium atom were charged in the atmosphere of nitrogeninto a stainless steel made up and down-stirring type autoclave havingan internal volume of 200 ml. The autoclave was purged with nitrogen gas(30 kg/cm² ·G) three times, and the temperature was raised to 120° C.under stirring after the internal pressure was restored to 0 kg/cm² ·G.Immediately after the temperature reached 120° C., water gas (H₂ /CO=1)was charged therein under pressure to a level of 50 kg/cm² ·G from apressurized chamber having an internal volume of 200 ml through asecondary pressure regulator to initiate reaction and the reaction wascontinued for 5 hours. The internal pressure was constantly maintainedat 50 kg/cm² ·G during the reaction.

After the reaction, the autoclave was cooled to room temperature and waspurged to normal pressure, and the reaction liquor was taken out. Aminor amount of the reaction liquor was subjected to gas chromatographyanalysis (column: Thermon-3000 Capirary Column 0.25φ×50 m manufacturedby Shimazu Seisakusho K. K.) to measure the concentration of theproduct. As this result, the tetradecene conversion was 89.5 mol % andthe C₁₅ aldehyde yield was 89.0 mol %, and the n/i C₁₅ aldehydeproduction ratio was 9.0.

Thereafter, the reaction liquor was distilled under reduced pressure toseparate the produced aldehyde. To the remaining liquor obtained afterthe distillation, were added 90 ml of the above 1-tetradecene and 10 mlof toluene, and the reaction was conducted at 120° C. for 5 hours undera pressure of 50 kg/cm² ·G in the same manner as in the first timereaction. As this results, the tetradecene conversion was 89.5 mol % andthe C₁₅ aldehyde yield was 88.7 mol %, and the n/i C₁₅ aldehydeproduction ratio was 9.0. Thus, as compared with the first timereaction, the activity of the catalyst was not deteriorated even afterrecycled and reused.

EXAMPLE 22

90 ml of 1-octene, 10 ml of toluene (gas chromatography internalstandard), 2.5 mg of Rh(acac) (CO)₂ and 50 mols of Phosphite CompoundNo. 14 per mol of rhodium atom were charged in the atmosphere ofnitrogen into a stainless steel made up and down-stirring type autoclavehaving an internal volume of 200 ml. The autoclave was purged withnitrogen gas (30 kg/cm² ·G) three times, and the temperature was raisedto 120° C. under stirring after the internal pressure was restored to 0kg/cm² ·G. Immediately after the temperature reached 120° C., water gas(H₂ /CO=1) was charged therein under pressure to a level of 50 kg/cm² ·Gfrom a pressurized chamber having an internal volume of 200 ml through asecondary pressure regulator to initiate reaction and the reaction wascontinued for 6 hours. The internal pressure was constantly maintainedat 50 kg/cm² ·G during the reaction.

After the reaction, the autoclave was cooled to room temperature and waspurged to normal pressure, and the reaction liquor was taken out. Aminor amount of the reaction liquor was subjected to gas chromatographyanalysis (column: C-BPl Capirary Column 0.25φ×50 m manufactured byShimazu Seisakusho K. K.) to measure the concentration of the product.As this result, the octene conversion was 88.0 mol % and the C₉ aldehydeyield was 87.0 mol %, and the n/i C₉ aldehyde production ratio was 10.8.

Thereafter, the reaction liquor was distilled under reduced pressure toseparate the produced aldehyde. To the remaining liquor obtained afterthe distillation, were added 90 ml of the above 1-octene and 10 ml oftoluene, and the reaction was conducted at 120° C. for 6 hours under apressure of 50 kg/cm² ·G in the same manner as in the first timereaction. As this results, the octene conversion was 89.0 mol % and theC₉ aldehyde yield was 88.5 mol %, and the n/i C₉ aldehyde productionratio was 10.8. Thus, as compared with the first time reaction, theactivity of the catalyst was not deteriorated even after recycled andreused.

As mentioned above, according to the present invention, since thehydroformylation reaction activity and the selectivity of the aimedproduct can be highly improved by getting the phosphite compound presentin the hydroformylation reaction, the hydroformylation reaction can beindustrially favorably conducted.

What is claimed is:
 1. A bisphosphite compound having Formula (II):##STR16## wherein R³, R⁴, R⁵ and R⁶ are each a β-naphthyl groupsubstituted at least in the 3-position by a C₁ -C₄ -alkyl group, whichmay be the same or different, and A² is a divalent hydrocarbon selectedfrom the group consisting of an aliphatic hydrocarbon group, acycloaliphatic hydrocarbon group and an aromatic hydrocarbon group, eachof which may have a substituent selected from the group consisting of aC₁ -C₅ -alkyl group, methoxy and methoxycarbonyl.
 2. The bisphosphitecompound according to claim 1, wherein A² in the formula (II) is a--Ar-- or --Ar--B--Ar-group wherein Ar is an arylene group and B is a--CR⁹ R¹⁰ --, --O--, --S--, or --CO-- group, wherein R⁹ and R¹⁰ are eacha group selected from the group consisting of a hydrogen atom, an alkylgroup, an aryl group, an arylalkyl group, an alkylaryl group and acycloalkyl group.
 3. The bisphosphite compound according to claim 2,wherein Ar is a phenylene group, a biphenylene group or a naphthylenegroup.
 4. The bisphosphite compound according to claim 1 wherein theβ-naphthyl group has a C₁ -C₅ -alkyl group as a substituent at the3-position and at the 6-position.